Wilson Daniel W N, Franco Mauricio P, Myers William K, McGrady John E, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Road Oxford OX1 3TA UK.
Department of Chemistry, University of Oxford, Centre for Advanced ESR, Inorganic Chemistry Laboratory South Parks Road Oxford OX1 3QR UK
Chem Sci. 2019 Dec 2;11(3):862-869. doi: 10.1039/c9sc05969e.
We report on the (-butyl)isocyanide-catalysed isomersation of a phosphaethynolato-borane, [B]OCP ([B] = ,'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1-1,3,2-diazaboryl), to its linkage isomer, a phosphaketenyl-borane, [B]PCO. Mechanistic insight into this unusual isomerisation was gained through a series of stoichiometric reactions of [B]OCP with isocyanides and theoretical calculations at the Density Functional Theory (DFT) level. [B]PCO decarbonylates under photolytic conditions to afford a novel boryl-substituted diphosphene, [B]P[double bond, length as m-dash]P[B]. This reaction proceeds a transient triplet phosphinidene which we have been able to observe spectroscopically by Electron Paramagnetic Resonance (EPR) spectroscopy.
我们报道了（-丁基）异氰化物催化的膦乙炔醇硼酸酯[B]OCP（[B]=，'-双（2,6-二异丙基苯基）-2,3-二氢-1,1,3,2-二氮杂硼基）异构化为其键合异构体磷杂烯酮硼酸酯[B]PCO的过程。通过[B]OCP与异氰化物的一系列化学计量反应以及密度泛函理论（DFT）水平的理论计算，对这种不寻常的异构化反应有了机理上的认识。[B]PCO在光解条件下脱羰基，得到一种新型的硼基取代双膦烯[B]P=P[B]。该反应通过一个瞬态三线态磷烯进行，我们已经能够通过电子顺磁共振（EPR）光谱对其进行光谱观测。
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